The present invention relates to new, herbicidally active, substituted n-pyridyl-nitrogen heterocycles, methods for the preparation thereof, compositions comprising these compounds, and the use thereof for weed control, especially in crops of cultivated plants, such as grain, cereals, maize, rice, cotton, soybeans, rape, sorghum, sugar cane, sugar beet, sunflowers, vegetables, plantations, and forage crops or for the inhibition of plant growth and for non-selective control of weeds.
N-Phenyl and N-pyridylpyrazole compounds and N-pyridyltetramethylenetriazolidinediones with a herbicidal action are described, for example, in EP-A-0 370 332, DE-A-3 917 469, DE-A-19 518 054, DE-A-19 530 606, U.S. Pat. Nos. 5,306,694 and 4,406,689.
Also known as herbicides are N-pyridylimides, N-(2-pyridyl)pyridazinones and 3-phenyluracils, as described for example in WO 92/00976, JP-A-58-213 776 and EP-A-0 438 209.
N-(Phenyl)tetrahydroimidazoles with a herbicidal action are described for example in U.S. Pat. No. 5,112,383.
New substituted n-pyridylnitrogen heterocycles have now been found with herbicidal and growth-inhibiting properties.
Accordingly, the invention relates to compounds of formula I 
wherein 
R1 is hydrogen, fluorine, chlorine, bromine or methyl;
R2 is C1-C4alkyl, C1-C4halogenalkyl, halogen, hydroxy, C1-C4alkoxy, C1-C4halogenalkoxy, nitro, amino or cyano;
R3 is cyano or R4C(O)xe2x80x94;
R4 is hydrogen, fluorine, chlorine, C1-C8alkyl, C2-C8alkenyl, C2-C8alkinyl, C3-C6cycloalkyl, C1-C8halogenalkyl, cyano-C1-C4alkyl, C2-C8halogenalkenyl, C1-C4alkoxy-C1-C4alkyl, C3-C6alkenyloxy-C1-C4alkyl, C1-C4alkylthio-C1-C4alkyl, phenyl, phenyl substituted once to three times by halogen, C1-C4alkyl or C1-C4halogenalkyl, benzyl, benzyl substituted once to three times on the phenyl ring by halogen, C1-C4alkyl or C1-C4halogenalkyl; or
R3 is R5X1C(O)xe2x80x94;
X1 is oxygen, sulfur, 
R5 is hydrogen, C1-C8alkyl, C3-C8alkenyl, C3-C8alkinyl, C3-C6cycloalkyl, C3-C6cycloalkyl-C1-C6alkyl, C1-C8halogenalkyl, C3-C8halogenalkenyl, cyano-C1-C4alkyl, C1C4alkoxy-C1-C4alkyl, C3-C6alkenyloxy-C1-C4alkyl, (oxiranyl)-CH2xe2x80x94, oxetanyl, C1-C4alkylthio-C1-C4alkyl, phenyl, phenyl substituted once to three times by halogen, C1-C4alkyl or C1-C4halogenalkyl, benzyl, benzyl substituted once to three times on the phenyl ring by halogen, C1-C4alkyl or C1-C4-halogenalkyl, phenyl-C2-C6alkyl, C1-C6alkyl-COxe2x80x94C1-C4alkyl, 
xe2x80x83R8X2C(O)xe2x80x94C1-C6-alkyl, 
xe2x80x83or R8X2C(O)xe2x80x94C3-C6cycloalkyl;
X2 is oxygen, sulfur, 
R8 is hydrogen, C1-C8alkyl, C3-C8alkenyl, C3-C8alkinyl, C3-C6cycloalkyl, C1-C8halogenalkyl C3-C8halogenalkenyl, cyano-C1-C4alkyl, C1-C4alkoxy-C1-C4alkyl, C3-C6alkenyloxy-C1-C4alkyl, (oxiranyl)-CH2xe2x80x94, oxetanyl, C1-C4alkylthio-C1-C4alkyl, phenyl, phenyl substituted once to three times by halogen, C1-C4alkyl or C1-C4halogenalkyl, benzyl, benzyl substituted once to three times on the phenyl ring by halogen, C1-C4alkyl or C1-C4halogenalkyl, or phenyl-C2-C6alkyl; R6, R7, R9 and R10 are independently of one another hydrogen, C1-C8alkyl, C3-C8alkenyl, C3-C8alkinyl, C1-C8halogenalkyl or benzyl; or
R3 is B1xe2x80x94C1-C8alkyl, B1xe2x80x94C2-C8alkenyl, B1xe2x80x94C2-C8alkinyl, B1xe2x80x94C1-C8halogenalkyl, B1xe2x80x94C2-C8halogenalkenyl, B1xe2x80x94C1-C4alkoxy-C1-C4alkyl, B1xe2x80x94C1-C4alkylthio-C1-C4alkyl or B1xe2x80x94C3-C6cycloalkyl;
B1 is hydrogen, cyano, hydroxy, C1-C8alkoxy, C3-C8alkenyloxy, R11X3C(O)xe2x80x94, C1-C4alkylcarbonyl or C1-C4halogenalkylcarbonyl;
X3 has the same meaning as X2;
R11 has the same meaning as R8; or
R3 is B2xe2x80x94C(R12)xe2x95x90CHxe2x80x94;
B2 is nitro, cyano or R13X4C(O)xe2x80x94;
R12 is cyano or R14X5C(O)xe2x80x94;
X4 and X5 have the same meaning as X2; and
R13 and R14 have the same meaning as R8; 
R15 is C1-C3alkyl, C1-C3halogenalkyl or amino;
R16 is C1-C3halogenalkyl, C1-C3alkyl-S(O)n1, C1-C3halogenalkyl-S(O)n1 or cyano; or
R16 and R15 together form a C3- or C4alkylene or C3- or C4alkenylene bridge which may be substituted by halogen, C1-C3halogenalkyl or cyano;
n1 is 0, 1 or 2;
R17 is hydrogen, C1-C3alkyl, halogen, C1-C3halogenalkyl or cyano; or
R17 and R16 together form a C3- or C4alkylene or C3- or C4alkenylene bridge which may be substituted by halogen, C1-C3halogenalkyl or cyano;
R18 is hydrogen, C1-C3alkyl, halogen or cyano;
R19 is C1-C3halogenalkyl; or
R19 and R18 together form a C3- or C4alkylene or C3- or C4alkenylene bridge which may be substituted by halogen, C1-C3halogenalkyl or cyano;
R20 is hydrogen or C1-C3alkyl or halogen; or
R20 and R19 together form a C3- or C4alkylene or C3- or C4alkenylene bridge which may be substituted by halogen, C1-C3halogenalkyl or cyano;
R21 is hydrogen, C1-C3alkyl, halogen, C1-C3halogenalkyl, R40Oxe2x80x94, R41S(O)n2, R42(R43)N,
R45(R46)Nxe2x80x94C(R44)xe2x95x90Nxe2x80x94, hydroxy, nitro or Nxe2x89xa1Cxe2x80x94Sxe2x80x94;
R40 is C1-C3alkyl, C1-C3halogenalkyl, C2-C4alkenyl, C3- or C4alkinyl or C1-C5alkoxycarbonyl-C1-C4alkyl;
R41 is C1-C4alkyl or C1-C4halogenalkyl;
n2 is 0, 1 or 2;
R42 is hydrogen, C1-C4alkyl, C1-C4halogenalkyl, C3-C6cycloalkyl, OHCxe2x80x94 or C1-C4alkylcarbonyl;
R43, R44, and R46 are independently of one another hydrogen or C1-C4alkyl;
R45 is C1-C4alkyl;
R22 is hydrogen, C1-C4alkyl, halogen, C1-C4halogenalkyl, C2-C4alkenyl, C3-C5halogenalkenyl, C3- or C4alkinyl, C1-C4alkoxy, C1-C4alkylcarbonyl, C1-C4halogenalkylcarbonyl, C2-C4alkenylcarbonyl, C2-C4halogenalkenylcarbonyl, C2-C4alkinylcarbonyl, C2-C4halogenalkinylcarbonyl, C1-C4alkylcarbamoyl, C1-C4alkylS(O)n3, C3- or C4alkinylS(O),n3, OHCxe2x80x94, nitro, amino, cyano or Nxe2x89xa1Cxe2x80x94Sxe2x80x94;
n3 is 0, 1 or 2;
R23 and R24 independently of one another are hydrogen, C1-C4alkyl, halogen, C1-C4halogenalkyl or cyano
R25 and R26 are independently of one another hydrogen, methyl, halogen, hydroxy or xe2x95x90O;
R27 and R28 are independently of one another hydrogen, C1-C4alkyl or C1-C4halogenalkyl;
R29 and R30 are independently of one another hydrogen, C1-C3alkyl or halogen;
R31 and R32 independently of one another are hydrogen or C1-C4alkyl; or
R31 and R32 together form the group 
R47 and R48 are independently of one another C1-C4alkyl; or
R47 and R48 together form a C4 or C5alkylene bridge;
R33 is hydrogen or C1-C3alkyl; or
R33 together with R32 forms a C3-C5alkylene bridge which may be broken by oxygen and/or substituted by halogen, C1-C4alkyl, C2-C4alkenyl, C1-C3alkylcarbonyloxy, C1-C3alkylsulfonyloxy, hydroxy or xe2x95x90O;
R34, R35, R36 and R37 are independently of one another hydrogen, C1-C3alkyl, C3- or C4alkenyl or C3-C5alkinyl; or
R34 and R35 on the one hand and R36 and R37 on the other each form a C2-C5alkylene or C3-C5alkenylene bridge, which may be broken by oxygen, xe2x80x94C(O)xe2x80x94, sulfur, or xe2x80x94S(O)2xe2x80x94;
R38 is hydrogen, C1-C4alkyl, C1-C4halogenalkyl, C3- or C4alkenyl or C3- or C4alkinyl;
R39 is hydrogen, C1-C4alkyl, C1-C3alkoxy-C1- or xe2x80x94C2alkyl, C1-C4halogenalkyl, C3- or C4alkenyl, C3- or C4halogenalkenyl or C3- or C4alkinyl; or
R39 and R38 together form a C3-C5alkylene bridge; and
X6, X7, X8, X9, X10, X11, X12, X13, X14, X15, X16, X17, X18 and X19 are independently of one another oxygen or sulfur,
and the agrochemically acceptable salts and stereoisomers of these compounds of formula I.
In the definitions listed hereinbefore, halogen is taken to mean iodine, preferably fluorine, chlorine and bromine.
The alkyl, alkenyl and alkinyl groups mentioned in the substituent definitions may be straight-chained or branched, as is also the case with the alkyl, alkenyl and alkinyl part of the alkylcarbonyl, alkylcarbonyloxy, alkylcarbonylalkyl, alkenyloxy, alkenyloxyalkyl, alkenylcarbonyl, alkinylcarbonyl, alkylcarbamoyl, hydroxyalkyl, cyanoalkyl, alkoxyalkyl, alkylthio, alkylthioalkyl, alkylthio-C(O)xe2x80x94, alkylS(O)n3, alkylsulfonyloxy, alkylaminocarbonyl, dialkylaminocarbonyl, alkylcarbonylalkyl, B1alkyl, B1alkenyl, B1alkinyl, HOC(O)alkyl, phenylalkyl and R8X2C(O)xe2x80x94C1-C6alkyl groups.
Alkyl groups are for example methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl and the various isomeric pentyl, hexyl, heptyl and octyl radicals. Preferred are methyl, ethyl, n-propyl, isopropyl and n-butyl.
Examples of alkenyls are vinyl, allyl, methallyl, 1-methylvinyl, but-2-en-1-yl, pentenyl, 2-hexenyl, 3-heptenyl and 4-octenyl, preferably alkenyl radicals with a chain length of 3 to 5 carbon atoms.
Examples of alkinyls are ethinyl, propargyl, 1-methylpropargyl, 3-butinyl, but-2-in-1-yl, 2-methylbutin-2-yl, but-3-in-2-yl, 1-pentinyl, pent-4-in-1-yl or 2-hexinyl, preferably alkinyl radicals with a chain length of 2 to 4 carbon atoms.
Alkyl groups substituted once or more, especially once to three times, by halogen are suitable as the halogenalkyl, the halogen being iodine, especially fluorine, chlorine and bromine, for example fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2-chloroethyl, 2,2-dichloroethyl, 2,2,2-trifluoroethyl, 2,2,2-trichloroethyl and pentafluoroethyl.
Suitable halogenalkenyls are alkenyl groups substituted once or more by halogen, the halogen being bromine, iodine and especially fluorine and chlorine, for example 2- and 3-fluoropropenyl, 2- and 3-chloropropenyl, 2- and 3-bromopropenyl, 2,3,3-trifluoropropenyl, 3,3,3-trifluoropropenyl, 2,3,3-trichloropropenyl, 4,4,4-trifluorobut-2-en-1-yl and 4,4,4-trichlorobut-2-en-1-yl. Of the alkenyl radicals substituted once, twice or three times by halogen, those with a chain length of 3 or 4 carbon atoms are preferred. The alkenyl groups may be substituted by halogen on saturated or unsaturated carbon atoms.
Suitable halogenalkinyls are for example alkinyl groups substituted by halogen, the halogen being bromine, iodine and especially fluorine and chlorine, for example 3-fluoropropinyl, 3-chloropropinyl, 3-bromopropinyl, 3,3,3-trifluoropropinyl and 4,4,4-trifluorobut-2-in-1-yl.
Alkylsulfonyl is for example methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, n-butylsulfonyl, isobutylsulfonyl, sec-butylsulfonyl, tert-butylsulfonyl; preferably methylsulfonyl and ethylsulfonyl.
Halogenalkylsulfonyl is for example fluoromethylsulfonyl, difluoromethylsulfonyl, trifluoromethylsulfonyl, chloromethylsulfonyl, trichloromethylsulfonyl, 2-fluoroethylsulfonyl, 2,2,2-trifluoroethylsulfonyl and 2,2,2-trichloroethylsulfonyl.
Halogenalkenylsulfonyl is for example 2- and 3-fluoropropenylsulfonyl, 2- and 3-chloropropenylsulfonyl, 2- and 3-bromopropenylsulfonyl, 2,3,3-trifluoropropenylsulfonyl, 2,3,3-trichloropropenylsulfonyl, 4,4,4-trifluorobut-2-en-1-yl-sulfonyl and 4,4,4-trichlorobut-2-en-1-yl-sulfonyl.
Cyanoalkyl is for example cyanomethyl, cyanoethyl, cyanoeth-1-yl and cyanopropyl.
Hydroxyalkyl is for example hydroxymethyl, 2-hydroxyethyl and 3-hydroxypropyl.
Alkylamino is for example methylamino, ethylamino and the isomeric propyl and butylamino.
Dialkylamino is for example dimethylamino, diethylamino and the isomeric dipropyl and dibutylamino.
Halogenalkylamino is for example chloroethylamino, trifluoroethylamino and 3-chloropropylamino.
Di(halogenalkyl)amino is for example di(2-chloroethyl)-amino.
Alkylcarbonyl is in particular acetyl and propionyl.
Halogenalkylcarbonyl is in particular trifluoroacetyl, trichloroacetyl, 3,3,3-trifluoropropionyl and 3,3,3-trichloropropionyl.
Alkenylcarbonyl is in particular vinylcarbonyl, allylcarbonyl, methallylcarbonyl, but-2-en-1-yl-carbonyl, pentenylcarbonyl and 2-hexenylcarbonyl.
Alkinylcarbonyl is in particular acetylenecarbonyl, propargylcarbonyl, 1-methylpropargylcarbonyl, 3-butinylcarbonyl, but-2-in-1-yl-carbonyl and pent-4-in-1-yl-carbonyl.
Alkoxy is for example methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy and tert-butoxy; preferably methoxy, ethoxy and isopropoxy.
Alkenyloxy is for example allyloxy, methallyloxy and but-2-en-1-yloxy.
Alkinyloxy is for example propargyloxy and 1-methylpropargyloxy.
Alkoxyalkyl is for example methoxymethyl, methoxyethyl, ethoxymethyl, ethoxyethyl, n-propoxymethyl, n-propoxyethyl, isopropoxymethyl and isopropoxyethyl.
Alkenyloxy is for example allyloxyalkyl, methallyloxyalkyl and but-2-en-1-yloxyalkyl.
Alkoxycarbonyl is for example methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, isopropoxycarbonyl and n-butoxycarbonyl, preferably methoxycarbonyl and ethoxycarbonyl.
Alkenyloxycarbonyl is for example allyloxycarbonyl, methallyloxycarbonyl, but-2-en-1-yl-oxycarbonyl, pentenyloxycarbonyl and 2-hexenyloxycarbonyl.
Alkinyloxycarbonyl is for example propargyloxycarbonyl, 3-butinyloxycarbonyl, but-2-in-1-yl-oxycarbonyl and 2-methylbutin-2-yl-oxycarbonyl.
Alkoxyalkoxycarbonyl is for example methoxymethoxycarbonyl, ethoxymethoxycarbonyl, ethoxyethoxycarbonyl, propoxymethoxycarbonyl, propoxyethoxycarbonyl, propoxypropoxycarbonyl and butoxyethoxycarbonyl.
Halogenalkoxy is for example fluoromethoxy, difluoromethoxy, trifluoromethoxy, 2,2,2-trifluoroethoxy, 1,1,2,2-tetrafluoroethoxy, 2-fluoroethoxy, 2-chloroethoxy and 2,2,2-trichloroethoxy.
The cycloalkyl radicals suitable as substituents are for example cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.
The cycloalkoxycarbonyl radicals suitable as substituents are for example cyclopropoxycarbonyl, cyclobutoxycarbonyl, cyclopentoxycarbonyl and cyclohexyloxycarbonyl.
Alkylthio is for example methylthio, ethylthio, propylthio and butylthio, as well as the branched isomers thereof.
Alkylthioalkyl is for example methylthioethyl, ethylthioethyl, methylthiopropyl and ethylthiopropyl.
Halogenalkylthiocarbonyl is for example fluoromethylthiocarbonyl, difluoromethylthiocarbonyl, trifluoromethylthiocarbonyl, 2,2,2-trifluoroethylthiocarbonyl, 1,1,2,2-tetrafluoroethylthiocarbonyl, 2-fluoroethylthiocarbonyl, 2-chloroethylthiocarbonyl and 2,2,2-trichloroethylthiocarbonyl.
Corresponding meanings may also be ascribed to the substituents in the listed definitions, such as, for example, halogenalkenylcarbonyl, halogenalkinylcarbonyl, R40Oxe2x80x94, R4C(O)xe2x80x94, R11X3C(O)xe2x80x94, R13X4C(O)xe2x80x94, R14X5C(O)xe2x80x94, R5X1C(O)xe2x80x94, R8X2C(O)-alkyl, R8X2C(O)-cycloalkyl, R41S(O)n2xe2x80x94, 
R42(R43)Nxe2x80x94, R45(R46)Nxe2x80x94C(R44)xe2x95x90Nxe2x80x94, B1alkyl, B1alkenyl, B1alkinyl, B1halogenalkyl, B1halogenalkenyl, B1alkoxyalkyl, B1alkylthioalkyl, B1cycloalkyl and B2xe2x80x94C(R12)xe2x95x90CHxe2x80x94.
In the definition of R5, the groups 
mean that the C1-C6alkyl-C(O)xe2x80x94 or C1-C6alkylene chain is in addition substituted by phenyl (C6H5) on one of the 4 or 6 carbon atoms, wherein the phenyl ring is substituted once to three times by halogen, C1-C4alkyl or C1-C4halogenalkyl, and the alkylene chain may be straight-chained or branched and may, for example, be methylene, ethylene, methylethylene, propylene, 1-methylpropylene and butylene.
In the definitions cyanoalkyl, alkylcarbonyl, alkenylcarbonyl, halogenalkenylcarbonyl, alkinylcarbonyl, alkoxycarbonyl, alkoxycarbonylalkyl and halogenalkylcarbonyl, the cyano- and carbonyl carbon atoms are not included in the upper and lower limits of the carbon number.
L in the reagents of formulae XII, XXI, XXIVa, XXIVb and XXXV is a leaving group, such as halogen, for example, preferably chlorine, bromine or iodine, C1-C3alkyl- or arylsulfonyloxy, preferably CH3SO2Oxe2x80x94 or 
or C1-C6alkylcarbonyloxy, preferably acetyloxy.
L1 in the reagent of formula XIII is a leaving group such as, for example, HOS(O)2Oxe2x80x94, 
L2 in the reagents of formulae XXVa and XXVc is a leaving group such as, for example, hydroxy, C1-C4alkoxy or halogen, preferably chlorine, bromine or iodine.
L3 in the reagent of formula XXXI is a leaving group such as chlorine or bromine, trichloromethoxy or 
L4 in the compounds of formulae II and III (reaction schemes 1 and 2) is a leaving group such as, for example, halogen, typically fluorine, chlorine or bromine or C1-C4alkyl- or phenylsulfonyl or C1-C4alkyl-, C1-C4halogenalkyl- or phenylsulfonyloxy.
R33 together with R32 (group W7) forms a C3-C5alkylene bridge which may be broken for example by oxygen and substituted by xe2x95x90O, and is illustrated by way of example in Tables 127 (compound of formula I127), 130 (compound of formula I130), 136 (compound of formula I136) and 137 (compound of formula I1137).
The invention relates also to the salts which the compounds of formula I with acidic hydrogen, especially the derivatives with carboxylic acid groups (for example, carboxyl-substituted alkyl, alkylene, alkenyl, alkinyl, alkoxyalkyl, alkylthioalkyl and cycloalkyl groups) may form with bases. These salts are, for example, alkali metal salts, such as sodium and potassium salts; earth alkali metal salts, such as calcium and magnesium salts; ammonium salts, i.e. unsubstituted ammonium salts and monosubstituted or polysubstituted ammonium salts, such as triethylammonium and methylammonium salts; or salts with other organic bases.
Salt-forming alkali metal and alkaline earth metal bases include the hydroxides of lithium, sodium, potassium, magnesium or calcium, those of sodium and potassium being especially preferred. Suitable salt-forming substances are described for example in WO 97/41112. Examples of amines suitable for forming ammonium salts are ammonia, as well as primary, secondary, and tertiary C1-C18alkylamines, C1-C4hydroxyalkylamines and C2-C4alkoxyalkylamines, typically methylamine, ethylamine, n-propylamine, isopropylamine, the four isomeric butylamines, n-amylamine, isoamylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, pentadecylamine, hexadecylamine, heptadecylamine, octadecylamine, methyl ethylamine, methyl isopropylamine, methyl hexylamine, methyl nonylamine, methyl pentadecylamine, methyl octadecylamine, ethyl butylamine, ethyl heptylamine, ethyl octylamine, hexyl heptylamine, hexyl octylamine, dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, di-n-amylamine, diisoamylamine, dihexylamine, diheptylamine, dioctylamine, ethanolamine, n-propanolamine, isopropanolamine, N,N-diethanolamine, N-ethylpropanolamine, N-butylethanolamine, allylamine, n-butenyl-2-amine, n-pentenyl-2-amine, 2,3-dimethylbutenyl-2-amine, dibutenyl-2-amine, n-hexenyl-2-amine, propylenediamine, trimethylamine, triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, triisobutylamine, tri-sec-butylamine, tri-n-amylamine, methoxyethylamine and ethoxyethylamine; heterocyclic amines such as pyridine, quinoline, isoquinoline, morpholine, thiomorpholine, piperidine, pyrrolidine, indoline, quinuclidine and azepine; primary arylamines such as anilines, methoxyanilines, ethoxyanilines, o-, m- and p-toluidines, phenylenediamines, benzidines, naphthylamines and o-, m- and p-chloroanilines; but especially triethylamine, isopropylamine and diisopropylamine.
The salts of compounds of formula I with basic groups, especially with basic pyridyl and pyrazolyl rings (W3 and W4), or of derivatives with amino groups, e.g. amino, alkylamino and dialkylamino groups in the definition of R2, W1 or W3 (R15, R21, R22) are, for example, salts with inorganic and organic acids, for example hydrogen halides, such as hydrofluoric acid, hydrochloric acid, hydrobromic acid or hydriodic acid, as well as sulfuric acid, phosphoric acid, nitric acid and organic acids, such as acetic acid, trifluoracetic acid, trichloroacetic acid, propionic acid, hydroxyethanoic acid, thiocyanic acid, citric acid, benzoic acid, oxalic acid, formic acid, benzenesulfonic acid, p-toluenesulfonic acid and methanesulfonic acid.
The presence of at least one asymmetric carbon atom in the compounds of formula I, for example in substituent R3=R5X1C(O)xe2x80x94, wherein R5 is a branched alkyl, alkenyl, halogenalkyl or alkoxyalkyl group, or R3=B1xe2x80x94C3-C6cycloalkyl, wherein for example B1 is C1-C8alkoxy or R11X3C(O)xe2x80x94, means that the compounds may occur both in single optically active isomers and also in the form of racemic mixtures. In the present invention, the active substances of formula I are understood to include both the pure enantiomers and the racemates or diastereomers.
If an aliphatic Cxe2x95x90C double bond is present (e.g. in substituent R3=B2xe2x80x94C(R12)xe2x95x90CHxe2x80x94), then geometric isomerism may occur. The present invention also relates to these isomers.
Compounds of formula I are preferred wherein R2 is methyl, halogen, hydroxy, nitro, amino or cyano.
Also preferred are compounds of formula I wherein W is the group 
and R15, R16, R17, X6 and X7 are as defined under formula I.
Especially preferred are those compounds wherein R15 is methyl; R16 is trifluoromethyl; R17 is hydrogen; and X6 and X7 are oxygen.
Likewise preferred are compounds of formula I wherein R1 is fluorine or chlorine; R2 is chlorine, bromine or cyano; and R3 is R5X1C(O)xe2x80x94, wherein R5 has the meaning defined under formula I; and X1 is oxygen or sulfur. Of these compounds, those wherein R2 is chlorine are especially important.
The method described in the invention for the preparation of compounds of formula I, 
wherein R1, R2, R3, A and W are as defined under formula I, is carried out by analogy with known methods, such as those described for example in WO 97/00246, WO 96/01254 and International Patent Application Number PCT/EP 97/06243, and comprises treating a compound of formula II 
wherein R1, R2 and W have the meanings indicated, and L4 is a leaving group such as halogen, either
a) in a suitable solvent, where appropriate in the presence of a base such as a trialkylamine, a palladium or nickel catalyst and a compound of formula V
R5xe2x80x94OHxe2x80x83xe2x80x83(V),
xe2x80x83wherein R5 is hydrogen or C1-C4alkyl, in an autoclave under positive pressure with carbon monoxide, or
b) in a suitable solvent in the presence of a tertiary amine, a palladium catalyst, and an olefin by means of the Heck reaction, or under said conditions by means of reaction with a Grignard reagent of formula Va
R3xe2x80x94Mg-halogenidexe2x80x83xe2x80x83(Va),
xe2x80x83wherein R3 is B1xe2x80x94C1-C8alkyl, B1xe2x80x94C2-C8alkenyl, B1xe2x80x94C2-C8alkinyl, B1xe2x80x94C1-C8halogenalkyl, B1xe2x80x94C2-C8halogenalkenyl, B1xe2x80x94C1-C4alkoxy-C1-C4alkyl, B1xe2x80x94C1-C4alkylthio-C1-C4alkyl or B1xe2x80x94C13-C6cycloalkyl and B1 is as defined under formula I, or in an inert solvent and in the presence of a catalyst, such as palladium-bis-triphenylphosphine dichloride (Pd(C6H5)2Cl2), in a manner analogous to that described in Synlett 1998, 1185, with a tin compound of formula Vb
(R3)4Snxe2x80x83xe2x80x83(Vb),
xe2x80x83wherein R3 has the meaning indicated, or
c) where applicable in an inert solvent at reaction temperatures of 20-300xc2x0 C. subjecting it to a cyanidation reaction, e.g. with an alkali metal cyanide or a cyanide whose metal ion belongs to the first or second subgroup of the periodic system, such as copper cyanide, in a manner analogous to that described in J. Het. Chem. 11, 397 (1974), or
d) first oxidizing it in a suitable solvent to form a compound of formula IV 
xe2x80x83and treating this in an inert solvent with dimethylcarbamoyl chloride and a cyanidation reagent, and then where applicable further functionalizing it according to the definitions of A and R3.
The method described in the invention for the preparation of compounds of formula I, 
wherein R1, R2, R3 and A are as defined under formula I, W is a W1 group 
and R15, R16, R17, X6 and X7 are as defined under formula I, corresponding to a compound of formula Ia in reaction scheme 2, is carried out by analogy with the known methods such as those described for example in EP-A-0 438 209 or DE-OS-19 604 229, and comprises reacting a compound of formula III 
wherein R1, R2 and R3 have the meanings indicated, and L4 is a leaving group, such as halogen, for example fluorine, chlorine or bromine, in the presence of an inert solvent and ammonia if necessary in an autoclave at temperatures of xe2x88x9210 to 180xc2x0 C. to form a compound of formula VI 
reacting this in the presence of a base and a solvent
a) with a chloroformate of formula VII 
xe2x80x83wherein X6 is as defined under formula I, to form a compound of formula VIII 
b) with oxalyl chloride, phosgene or thiophosgene to form a compound of formula IX 
xe2x80x83followed by cyclization of a compound of formula VIII or IX in the presence of 0.1-1.5 equivalents of a base in an inert solvent with an enamine dervivative of formula X 
xe2x80x83wherein R16 and R17 are as defined under formula I, and X7 is oxygen, and a resulting compound of formula XI 
xe2x80x83wherein R1, R2, R3, R16, R17, X6 and X7 have the meanings indicated, and further reacting this compound in the presence of an inert solvent and a base with
c) a compound of formula XII
R15xe2x80x94Lxe2x80x83xe2x80x83(XII),
xe2x80x83wherein R15 is C1-C3alkyl or C1-C3halogenalkyl, and L is a leaving group, or
d) with a hydroxylamine derivative of formula XIII
NH2xe2x80x94L1xe2x80x83xe2x80x83(XIII),
xe2x80x83wherein L1 is a leaving group, and subsequently performing if necessary oxidation 
xe2x80x83and thionization.
The method described in the invention for the preparation of compounds of formula I, 
wherein R1, R2, R3, and A are as defined under formula I, W is a W2 group 
and R18, R19, R20, and X8 are as defined under formula I, corresponding to a compound of formula Ib in reaction scheme 3, is carried out by analogy with known methods, such as those described for example in DE-A-4 423 934 and JP-A-58 213 776, and comprises either
a) reacting a compound of formula III, 
xe2x80x83wherein R1, R2 and R3 have the meanings indicated, and L4 is a leaving group such as halogen, for example fluorine, chlorine or bromine, with hydrazine, preferably in an amphiprotic solvent, to form a compound of formula XIV 
xe2x80x83further reacting this with a compound of formula XV or XVa 
xe2x80x83wherein R18 and R19 have the meanings defined under formula I, and Hal in a compound of formula XVa is chlorine or bromine, or
b) first diazotizing a compound of formula VI, 
xe2x80x83wherein R1, R2 and R3 have the meanings indicated, then further reacting it with a compound of formula XVI 
xe2x80x83wherein R18 and R19 have the meanings indicated, and obtaining a compound of formula XVII 
xe2x80x83which if necessary is cyclized in the presence of a base, such as 4-dimethylaminopyridine and a compound of formula XVIII 
xe2x80x83wherein R20 has the meaning indicated, and X8 is oxygen, and subsequently performing if necessary oxidation 
The method described in the invention for the preparation of compounds of formula I, 
wherein R1, R2, R3 and A are as defined under formula I, W is a W7 group 
(W7), and R31, R32, R33, and X8 are as defined under formula I, corresponding to a compound of formula Ig in reaction scheme 4, is carried out by analogy with known methods, such as those described for example in EP-A-0 272 594, EP-A-0 493 323, DE-A-3 643 748, WO 95/23509, U.S. Pat. Nos. 5,665,681 and 5,661,109, and comprises for example either
a) reacting a compound of formula VIIIa 
xe2x80x83in the presence of a solvent and a base, or
b) a compound of formula IXa 
xe2x80x83if necessary in a suitable solvent, wherein the radicals R1, R2, R3 and X14 in compounds of formula VIIIa and IXa have the meanings indicated, with a compound of formula XIX 
xe2x80x83wherein R31, R32, R33 and X13 have the meanings indicated, and obtaining a compound of formula XX 
xe2x80x83cyclizing this in the presence of a suitable solvent and a base and then where applicable
c) if R33 is hydrogen, reacting it with a compound of formula XXI
R33xe2x80x94Lxe2x80x83xe2x80x83(XXI),
xe2x80x83wherein R33 is C1-C3alkyl, and L is a leaving group, and subsequently performing if necessary oxidation 
xe2x80x83and thionization.
The method described in the invention for the preparation of compounds of formula I, 
wherein R1, R2, R3 and A are as defined under formula I, W is a W8 group 
(W8), and R34, R35, X15, and X16 are as defined under formula I, corresponding to a compound of formula Ih in reaction scheme 5, is carried out by analogy with known methods, such as those described for example in EP-A-0 210 137, DE-A-2 526 358, EP-A-0 075 267 and EP-A-0 370 955, and comprises
a) reacting a compound of formula VIIIb 
xe2x80x83in the presence of a solvent and a base, or
b) a compound of formula IXb 
xe2x80x83wherein the radicals R1, R2, R3 and X15 in compounds of formula VIIIb and IXb have the meanings indicated, if necessary in a suitable solvent, with a compound of formula XXII 
xe2x80x83wherein R34, R35, and X16 have the meanings indicated, and obtaining a compound of formula XXIII 
xe2x80x83cyclizing this in the presence of a suitable solvent and a base and then where applicable
c) if R34 and/or R35 are/is hydrogen, further reacting it with a compound of formula XXIVa or XXIVb
R34xe2x80x94Lxe2x80x83xe2x80x83(XXIVa)
xe2x80x83or
R35xe2x80x94Lxe2x80x83xe2x80x83(XXIVb),
xe2x80x83wherein R34 and R35 are independently C1-C3alkyl, and L is a leaving group, or with a Michael acceptor, and then if necessary oxidizing 
xe2x80x83and thionizing it.
The method described in the invention for the preparation of compounds of formula I, 
wherein R1, R2, R3 and A are as defined under formula I, W is a W3 group 
(W3), and R21, R22, and R23 are as defined under formula I, corresponding to a compound of formula Ic in reaction scheme 6, is carried out by analogy with known methods, such as those described for example in WO 97/07114, U.S. Pat. No. 5,306,694, DE-A-3 832 348, EP-A-0 257 479 and EP-A-0 500 209, and comprises condensing a compound of formula XIV 
wherein R1, R2 and R3 have the meanings indicated, for example
a) with a compound of formula XXV 
xe2x80x83wherein R21 is hydrogen, C1-C3alkyl or C1-C3halogenalkyl; R22 is hydrogen, C1-C4alkyl, C1-C4halogenalkyl, C2-C4alkenyl, C3-C5halogenalkenyl or C3- or C4alkinyl; and R23 hydrogen, C1-C4alkyl or C1-C4halogenalkyl, if necessary in the presence of an acidic, basic or bifunctional catalyst such as p-toluenesulfonic acid, for example, or
b) with a compound of formula XXVa 
xe2x80x83wherein R22 and R23 have the meanings indicated, and L2 is a suitable leaving group, to form a compound of formula XXVI 
xe2x80x83and further functionalizing the pyrazolone group in accordance with the definition of R21 in a manner analogous to known methods, for example using a halogenation agent such as phosphorus oxychloride, to form the corresponding halogen derivative of formula Ic 
xe2x80x83wherein R1, R2, R3, R22 and R23 have the meanings indicated, and R21 is halogen, and subsequently performing if necessary oxidation 
The method described in the invention for the preparation of compounds of formula I, 
wherein R1, R2 R3 and A are as defined under formula I, W is a W4 group 
and R24, R25, R26 are as defined under formula I, corresponding to formula Id in reaction scheme 7, is carried out by analogy with known methods such as those described for example in EP-A-0 370 332, EP-A-0 370 955 or DE-A-3 917 469, and comprises condensing a compound of formula XIV 
wherein R1, R2 and R3 have the meanings indicated,
a) with a compound of formula XXVb 
xe2x80x83wherein R25 and R26 have the meanings indicated, and R24 is hydrogen, C1-C4alkyl or C1-C4halogenalkyl, if necessary in the presence of a catalyst, or
b) with a compound of formula XXVc 
xe2x80x83wherein R25 and R26 have the meanings indicated, and L2 is a suitable leaving group, to form a compound of formula XXVIa 
xe2x80x83and treating this compound with a halogenation agent, such as phosphoroxy halogenide or thionyl halogenide, and obtaining a compound of formula Id 
xe2x80x83wherein R1, R2, R3, R25 and R26 have the meanings indicated and R24 is halogen, and reacting this compound if necessary with a cyanide of formula XXVII
M(CN)sxe2x80x83xe2x80x83(XXVII),
xe2x80x83wherein M is an ammonium cation, alkali metal ion or metal ion of the first or second subgroup of the periodic system, and s is the number 1 or 2, where applicable in the presence of an alkali metal iodide (R24=cyano; reaction scheme 7), and subsequently performing if necessary oxidation 
The method described in the invention for the preparation of compounds of formula I, 
wherein R1, R2, R3 and A are as defined under formula I, W is a W5 
or W6 
group, and R27, R28, R29, R30, and X9 to X12 are as defined under formula I, corresponding to compounds of formula Ie and If in reaction scheme 8, is carried out by analogy with known methods, such as those described for example in DE-A-3 917 469, WO 92/00976, U.S. Pat. No. 5,069,711 and EP-A-0 260 228, and comprises for example
a) reacting a compound of formula XXVIII 
b) a compound of formula XXVIIIa 
xe2x80x83wherein radicals R27 to R30 in compounds of formulae XXVIII and XXVIIIa have the meanings indicated, with a compound of formulae VI 
xe2x80x83wherein R1, R2 and R3 have the meanings indicated, in an inert solvent in the presence of a C1-C4alkylcarboxylic acid at temperatures of 20xc2x0 to 200xc2x0 C. and reacting the resulting compounds of formulae Ie and If 
xe2x80x83wherein R1 to R3 and R27 to R30 have the meanings indicated, and X9 to X12 are oxygen, if necessary with the aid of a suitable sulfur reagent to form the corresponding thiono compound of formulae Ie and If, wherein X9 and/or X10, X11, X12, are sulfur, and oxidizing the said compound 
xe2x80x83reaction scheme 8).
The method described in the invention for the preparation of compounds of formula I 
wherein R1, R2, R3, and A are as defined under formula I, W is a W9 group 
and R36, R37, X17, and X18 are as defined under formula I, corresponding to a compound of formula Ii in reaction scheme 9, is carried out by analogy with known methods, such as those described for example in WO 95/00521, EP-A-0 611 708 and WO 94/25467, and comprises for example reacting
a) a compound of formula VIIIc 
b) a compound of formula IXc 
xe2x80x83wherein the radicals R1, R2, R3 and X18 in compounds of formulae VIIIc and IXc have the meanings indicated, if necessary in the presence of a suitable solvent and a base, with a compound of formula XXIX
R37xe2x80x94NHxe2x80x94NHxe2x80x94R36xe2x80x83xe2x80x83(XXIX),
xe2x80x83wherein R36 and R37 are as defined under formula I, and obtaining a compound of formula XXX 
xe2x80x83and subsequently reacting this, if necessary in a solvent and in the presence of a base, with a (thio-)carbonylation reagent of formula XXXI 
xe2x80x83wherein X17 has the meaning indicated, and L3 is a leaving group (reaction scheme 9), and subsequently performing if necessary oxidization 
The method described in the invention for the preparation of compounds of formula I 
wherein R1, R2, R3 and A are as defined under formula I, W is a W10 group 
and R38 R39, and X9 are as defined under formula I, corresponding to a compound of formula Ik in reaction scheme 10, is carried out by analogy with known methods, such as those described for example in U.S. Pat. No. 5,980,480, DE-A-3 917 469, U.S. Pat. No. 4,818,275, 5,041,155 und EP-A-0 610 733, and comprises, for example,
a) reacting a compound of formula XIV 
xe2x80x83if necessary in the presence of a catalyst, with a compound of formula XXXII 
xe2x80x83to form a compound of formula XXXIII 
xe2x80x83wherein the radicals R1, R2, R3 and R39 in the compounds of formulae XIV, XXXII and XXXIII have the meanings indicated, and further cyclizing this compound with an azide of formula XXXIV 
xe2x80x83(X19xe2x95x90O, R38xe2x95x90H), or
b) cyclizing a compound of formula XIV 
xe2x80x83with a compound of formula XXXVI 
xe2x80x83wherein the radicals R1, R2, R3 and R39 in the compounds of formulae XIV and XXXVI have the meanings indicated, (X19xe2x95x90O, R38xe2x95x90H), or
c) cyclizing a compound of formula XIV 
xe2x80x83first with a compound of formula XXXVII
R39xe2x80x94CHOxe2x80x83xe2x80x83(XXXVII)
xe2x80x83to form a compound of XXXIIIa 
xe2x80x83then with an alkali metal cyanate to form a compound of XXXVIII 
xe2x80x83and finally cyclizing this compound in the presence of an oxidation agent and obtaining a compound of formula Ik 
xe2x80x83wherein R1, R2, R3 and R39 have the meanings indicated, X19 is oxygen, and R38 is hydrogen, and treating this compound if necessary with a sulfur reagent (X19xe2x95x90S) and in the presence of a base with an alkylation reagent of formula XXXV
R38xe2x80x94Lxe2x80x83xe2x80x83(XXXV),
xe2x80x83wherein R38 is C1-C4alkyl, C1-C4halogenalkyl, C3- or C4alkenyl, C3- or C4halogenalkenyl or C3- or C4alkinyl, and L is a leaving group, and subsequently performing if necessary oxidization 
xe2x80x83and thionization.
The method described in the invention for the preparation of compounds of formula I is carried out in a manner analogous to known methods and comprises, for example, reacting a compound of formula III 
wherein R1, R2 and R3 are as defined under formula I, and L4 is a leaving group, such as halogen, for example fluorine, chlorine or bromine, with a compound of W01, W02, W03, W04, W05, W06, W07, W08, W09 or W010 
wherein R15 to R39 and X6 to X19 are as defined under formula I, if necessary in the presence of a suitable solvent and base, and if necessary subjecting the obtainable compounds of formula I (Axe2x95x90Nxe2x80x94) to oxidation 
and thionization.
The method described in the invention for the preparation of compounds of formula II 
wherein R1 and R2 are as defined under formula I, W is a 
group; R21 to R30, R36 to R39, X9 to X12 and X17 to X19 are as defined under formula I, and L4 is a leaving group, such as halogen for example, especially chlorine or bromine, is carried out in a manner analogous to known methods and comprises, for example, first oxidizing a compound of formula XXXIX 
in a suitable solvent to form a compound of formula XXXX 
wherein radicals R1, R2 and W in the compounds of formulae XXXIX and XXXX have the meanings indicated, and then subjecting the compound either to
a) halogenation, for example with phosphorus oxychloride, if necessary in the presence of a base and a suitable solvent, or
b) transformation in an inert solvent in the presence of an anhydride or antimony pentachloride, and following aqueous treatment, to form a compound of XXXXI 
xe2x80x83(so-called Katada reaction), and the halogenation of this compound if necessary in the presence of a base and a suitable solvent as described under variant a).
The above methods of preparation are explained in more detail in the following reaction schemes 1 to 12.
The preparation of a compound of formula I 
wherein R1 to R3, A and W are as defined under formula I, is explained in the following reaction scheme 1: 
The pyridine derivatives of formula I, wherein R3 is a HOOCxe2x80x94 or R5OOC group, may be prepared according to variant a) in reaction scheme 1 in a manner analogous to known methods, a useful method being to react for example the 6-halogen pyridine (L4=halogen) of formula II in the presence of a palladium or nickel catalyst, such as a palladium triphenylphosphine complex (PdCl2(PPh3)2), with carbon monoxide under pressure in an autoclave, if necessary in the presence of an alcohol of formula V
R5xe2x80x94OHxe2x80x83xe2x80x83(V)
and a base, such as a trialkylamine, for example triethylamine.
According to variant b) in reaction scheme 1, pyridine derivatives of formula I, wherein R3 is a B1xe2x80x94C2-C8alkenyl, B1xe2x80x94C2-C8alkinyl or B2xe2x80x94C(R12)xe2x95x90CH group, are obtainable in a manner analogous to known methods, such as those described in xe2x80x9cTransition Metals in Organic Synthesisxe2x80x9d, Editor S. Gibson, Oxford Press, 1997, for example starting from a 6-halogen pyridine of formula II (L4=halogen) under the conditions of the Heck reaction with an olefin in the presence of a palladium catalyst, such as palladium(II) acetate (Pd(CH3COO)2), a tertiary amine, such as triethylamine, and a solvent.
According to variant c) in reaction scheme 1, pyridine derivatives of formula I, wherein R3 is a cyano group, are obtainable for example directly by reacting for example the 6-halogen pyridine of formula II (L4=halogen) with a cyanidation reagent such as an alkali metal cyanide, for example potassium or sodium cyanide, a transition metal cyanide, for example copper cyanide, a tetraalkylammonium cyanide or trialkylsilyl cyanide, for example trimethylsilyl cyanide, in an inert solvent.
According to variant d) in reaction scheme 1, a reactivation for example of the 6-halogen pyridine of formula II (L4=halogen) first takes place via oxidation to form the corresponding pyridine-N-oxide of formula IV and the reaction thereof with dimethylcarbamoyl chloride to form the reactive 1-carbamoyloxypyridinium salt. The following reaction of this pyridinium salt with a cyanidation reagen is carried out in a manner analogous to that described under c). Such cyanidation reactions are described for example in Heterocycles 22,1121 (1984), J.Org.Chem. 48, 1375 (1983) and U.S. Pat. No. 4,776,219.
Further derivatization of the pyridine derivatives of formula I, primarily obtainable according to variants a) to d) in reaction scheme 1, wherein R3 is a carboxyl, alkoxycarbonyl, alkenyl or alkinyl, or cyano group, and A is nitrogen, can be readily accomplished, taking into account the chemical reactivities of the pyridyl and W parts (groups W1 to W10), in a manner analogous to known standard methods, such as esterification, transesterification, hydrolysis, oxidative or reductive processes, or condensation reactions, for example the Wittig-Horner reaction. Such standard methods are described for example in WO 93/06090, EP-A-0 240 659 and in Houben-Weyl, xe2x80x9cMethoden der Organischen Chemiexe2x80x9d, Vol. E1, Thieme Verlag Stuttgart, 1982.
The preparation of a compound of formula Ia 
wherein R1, R2, R3, R15, R16, R17, X6 and X7 are as defined under formula I, is explained in the following reaction scheme 2. 
For the preparation of the compounds of formula Ia according to the invention, many known standard methods are available, such as those described for example in EP-A-0 438 209 and DE-OS-19 604 229 (R16=Cyano). In reaction scheme 2, a selection of suitable preparative processes is shown, wherein the choice of reaction pathways and reagents depends on the reactivities of the substituents in the intermediate stages.
Starting for example from a compound of formula III, the aminopyridine of formula VI can be obtained by reacting with ammonia in an inert solvent, if necessary in an autoclave at temperatures from xe2x88x9210 to 180xc2x0 C. This aminopyridine can be reacted in the presence of a base and a solvent either
a) with a chloroformate of formula VII (X6xe2x95x90O or S) to form a pyridyl carbamate of formula VIII, or
b) with oxalyl chloride, phosgene (X6xe2x95x90O) or thiophosgene (X6xe2x95x90S) to form an iso(thio)cyanate of formula IX. Such reactions are described for example in Angew. 1971, 407.
The carbamate and iso(thio)cyanate of formulae VIII and IX can be cyclized in the presence of the enamine derivative of formula X in an inert solvent to form the uracil derivative of formula XI, the reaction of the iso(thio)cyanate of formula IX being advantageously carried out in the presence of 0.1-1.5 equivalents of a base, for example sodium hydride, potassium tert-butylate or alkaline earth metal oxide or hydroxide, for example barium hydroxide.
The desired compounds of formula Ia can be prepared from the uracils of formula XI, according to standard methods, in the presence of an inert solvent and at least 1 equivalent of a base, for example an alkali metal carbonate such as potassium carbonate,
c) with an alkylation agent of formula XII to form an N-alkyl derivative of formula Ia (R15=alkyl), or
d) in analogy to WO 97/05116 with a hydroxylamine derivative of formula XIII, wherein L1 is a leaving group such as HOS(O)2Oxe2x80x94, 
xe2x80x83for example 2,4-dinitrophenylhydroxylamine or hydroxylamine-O-sulfonic acid, to form the N-amino derivative of formula Ia (R15=amino). The desired thiono derivatives of formula Ia (X6, X7xe2x95x90S) can be obtained by thionization, for example with phosphorus pentasulfide or Lawesson""s reagent.
The preparation of a compound of formula Ib 
wherein R1, R2, R3, R18, R19, R20, and X8 are as defined under formula I, is explained in the following reaction scheme 3. 
The compounds of formula Ib can be prepared according to known methods, for example according to reaction scheme 3 (variant a)) by reacting a 2-halogen pyridine derivative of formula III (L4=halogen) with hydrazine, preferably in an amphiprotic solvent, such as alcohols, by analogy with GB-A-2 230 261, to form the 2-hydrazino derivative of formula XIV.
This is reacted with a diketone of formula XV, by analogy with DE OS-19754348, or with a dihalogen ketone of formula XVa, by analogy with WO 97/07104, to form the hydrazone derivative of formula XVII.
Subsequent cyclization to the desired compound of formula Ib takes place in the presence of the phosphoran derivative of formula XVIII, if necessary in the presence of a base, for example 4-dimethylaminopyridine. If X8xe2x95x90O in a compound of formula Ib, then thionization can subsequently be carried out in a manner similar to that described under reaction scheme 2(X8xe2x95x90S).
According to reaction scheme 3, the hydrazone derivative of formula XVII can also be obtained from the 2-aminopyridine derivative of formula VI by means of diazotization, preferably under exclusion of water, and subsequent coupling with the keto acid of formula XVI (Japp-Klingemann reaction similar to that described under DE-OS-19754348)xe2x80x94(variant b) in reaction scheme 3).
The preparation of a compound of formula Ig 
wherein R1, R2, R3, R31, R32, R33, and X14 are as defined under formula I, is explained in the following reaction scheme 4. 
Compounds of formula Ig can be prepared in a manner analogous to known methods, as described, for example, in EP-A-0 272 594, EP-A-0 493 323, DE-A-3 643 748, WO 95/23509, U.S. Pat. No. 5,665,681 or U.S. Pat. No. 5,661,109.
For example, according to reaction scheme 4, either
a) a carbamate derivative of formula VIIIa in the presence of a solvent and a base, or
b) an iso(thio-)cyanate of formula IXa, if necessary in a suitable solvent, can be cyclized with an amino acid derivative of formula XIX via a compound of formula XX in the presence of a base and a suitable solvent to form a compound of formula Ig.
For those cases (variant c)) where, in a compound of formula Ig, R33 is hydrogen and X13 and/or X14 are/is oxygen, alkylation can subsequently be carried out, if necessary with an alkylation reagent of formula XXI, on the free N-atom of the hydantoin ring and the ring carbonyl group then thionized (X13 and/or X14xe2x95x90S).
The preparation of a compound of formula Ih 
wherein R1, R2, R3, R34, R35, X15, and X16 are as defined under formula I, is explained in the following reaction scheme 5. 
Compounds of formula Ih can be prepared in a manner analogous to known methods, as described for example in EP-A-0 210 137, DE-OS-2 526 358, EP-A-0 075 267 or EP-A-0 370 955.
For example, according to reaction scheme 5, either
a) a carbamate derivative of formula VIIIb in the presence of a solvent and a base, or
b) an iso(thio-)cyanate of formula IXb, if necessary in a suitable solvent, can be cyclized with a carbazate of formula XXII via a compound of formula XXIII in the presence of a base and a suitable solvent to form a compound of formula Ih.
For those cases (variant c)) where, in a compound of formula Ih, R34 and/or R35 are/is hydrogen and X15 and/or X16 are/is oxygen, alkylation can subsequently be carried out with an alkylation reagent of formula XXIVa or XXIVb on the free N-atoms and the ring carbonyl groups then thionized with a thionization reagent (X15 and/or X16xe2x95x90S).
For the preparation of compounds of formula Ih in reaction scheme 5, wherein R34 and R35 together form an alkylene bridge which is broken for example by xe2x80x94S(O)2xe2x80x94, a compound of formula Ih, wherein R34 and R35 are hydrogen, can be reacted for example with an appropriate Michael acceptor, e.g. CH2xe2x95x90CHxe2x80x94S(O)2CH3 or CH2xe2x95x90CHxe2x80x94S(O)2xe2x80x94CHxe2x95x90CH2, and the resulting Michael addition products then functionalized.
The preparation of a compound of formula Ic 
wherein R1, R2, R3, and R21 to R23 are as defined under formula I, is explained in the following reaction scheme 6. 
According to reaction scheme 6, the pyrazol compounds of formula Ic can be prepared e.g. either from the hydrazinopyridine derivatives of formula XIV by means of condensation with a 1,3-dicarbonyl derivative of formula XXV (variant a)), or by means of condensation with a xcex2-carbonylcarboxylic acid derivative of formula XXVa, where L2 is a leaving group, such as C1-C4alkoxy, hydroxy or halogen, for example chlorine or bromine (variant b)), and subsequent treatment of the resulting pyridylpyrazolone derivative of formula XXVI with a halogenation agent, for example phosphorus oxychloride (R21=halogen). The two reaction steps a) and b) in reaction scheme 6 are carried out if necessary in the presence of an acidic, basic or bifunctional catalyst, such as p-toluenesulfonic acid.
The compounds of formula Ic obtained in this way can be further functionalized using standard methods according to the definition of substituents R21 to R23.
Compounds of formula Ic in reaction scheme 6, wherein R22 is hydrogen, can be further functionalized according to the definition of R22, e.g. using an electrophilic reagent, for example a halogenation agent, such as an elementary halogen or sulfurylhalogenide, to form the corresponding compounds of formula Ic, wherein R22 is halogen, or using a nitrating agent such as nitric acid in a mixture with a further strong acid, such as sulfuric acid, to form the corresponding compounds of formula Ic, wherein R22 is nitro.
The preparation of a compound of formula Id 
wherein R1, R2, R3, and R24 to R26 are as defined under formula I, is explained in the following reaction scheme 7. 
According to reaction scheme 7, the tetrahydroindazol compounds of formula Id can be obtained by known methods from the hydrazinopyridine derivatives of formula XIV, for example either by means of condensation with a cyclohexanone derivative of formula XXVb acylated in the 2-position, wherein R24 is as defined under formula I, except where R24 is halogen or cyano (variant a)), or by means of condensation with a cyclohexanone derivative of formula XXVc, wherein L2 is a leaving group, such as C1-C4alkoxy, hydroxy or halogen, for example chlorine or bromine, and subsequent halogenation (variant b)) in a manner analogous to that described under reaction scheme 6.
The halogen derivatives of formula Id, wherein R24 is halogen, can be reacted according to known methods with an alkali metal, ammonium or metal cyanide, wherein the metal ion is selected from the first or second subgroup of the periodic system, if necessary with the addition of an alkali metal iodide, to form the corresponding cyano-substituted derivatives pf formula Id (R24xe2x95x90CN).
The preparation of compounds of formulae Ie and If 
wherein R1, R2, R3, R27 to R30 and X9 to X12 are as defined under formula I, is explained the following reaction scheme 8. 
According to reaction scheme 8, the pyrrolindione derivatives of formula Ie and the tetrahydroisoindolindione derivatives of formula If can be obtained in a manner analogous to known methods, for example by reacting an anhydride of formula XXVIII (variant a)) and/or XXVIIIa (variant b)) with an aminopyridine of formula VI in an inert solvent, such as ether, for example dioxan, or a lower alkylcarboxylic acid, for example propionic acid, at temperatures of 20-200xc2x0 C.
The compounds of formulae Ie and If (X9 to X12xe2x95x90O) which are obtainable according to reaction scheme 8 can be thionized if necessary with a suitable sulfur reagent (X9 to X12xe2x95x90S).
The preparation of a compound of formula Ii 
wherein R1, R2, R3, R36, R37, X17, and X18 are as defined under formula I, is explained following reaction scheme 9. 
According to reaction scheme 9, compounds of formula Ii can be prepared by known methods, for example by first reacting a carbamate of formula VIIIc (variant a)) and/or an isothiocyanate of formula IXc (variant b)) with a hydrazine derivative of formula XXIX to form the semicarbazide derivative of formula XXX, and then cyclizing this derivative in the presence of a carbonylation or thiocarbonylation reagent of formula XXXI. Both reaction steps are usefully accomplished in a suitable solvent and in the presence of a base. A suitable (thio)carbonylation reagent of formula XXXI is for example phosgene, diphosgene, thiophosgene or carbonyidiimidazol. L3 in a compound of formula XXXI is therefore a leaving group such as a halogen, for example, chlorine or bromine, trichloromethoxy or 
The preparation of a compound of formula Ik 
wherein R1, R2, R3, R38, R39, and X19 are as defined under formula I, is explained in the following reaction scheme 10. 
According to reaction scheme 10, the triazolone derivatives of formula Ik can be prepared in a manner analogous to known methods, starting for example from the hydrazinopyridine derivative of formula XIV, which according to variant a) is usefully reacted with a keto acid of formula XXXII in the presence of an acid catalyst, such as a lower alkylcarboxylic acid, for example propionic acid, a mineral acid, for example sulfuric acid or hydrochloric acid, or a sulfonic acid, for example p-toluenesulfonic acid, to form a hydrazone derivative of formula XXXIII. This can subsequently be cyclized with an azide of formula XXXIV to form a triazolone derivative of formula Ik, wherein X19 is oxygen, and R38 is hydrogen, and then further derivatized if necessary according to standard methods using an alkylation reagent of formula XXXV or a sulfur reagent.
According to variant b), the hydrazinopyridine derivative of formula XIV can be cyclized with an iminoether of formula XXXVI to form a triazolone derivative of formula Ik, wherein X19 is oxygen, and R38 is hydrogen, and then if necessary alkylated or thionized as described under variant a).
According to variant c) in reaction scheme 10, the hydrazinopyridine derivative of formula XIV can be reacted first with an aldehyde of formula XXXVII and then, in the presence of a lower alkylcarboxylic acid, such as acetic acid, with an alkali metal cyanate to form a compound of formula XXXVIII which, if necessary, is not isolated, and finally cyclized with an oxidizing agent, such as alkali metal hypochlorite (Javelle) to form a compound of formula Ik, wherein X19 is oxygen, and R38 is hydrogen. If necessary, the resulting compound of formula Ik can be alkylated or thionized, as described under variant a).
In certain cases, compounds of formula I can also be usefully obtained in a manner analogous to that described in J. Het. Chem. 15, 1221 (1978) by the substitution of a 2-halogen pyridine of formula III (L4=halogen), if necessary in the presence of a suitable solvent and a base, with the desired heterocycles of formulae W01 to W010
or alkali metal salts thereof, as illustrated with the example of a compound of formula Ic in reaction scheme 11. 
The intermediate products of formula II 
wherein R1 and R2 are as defined under formula I, L4 is a leaving group, such as halogen or C1-C4alkyl or phenylsulfonyl, and W is a W3, W4, W5, W6, W9 or W10 group, are new. The invention thus also relates to these compounds.
The preparation of compounds of formula II is explained in reaction scheme 12. 
The pyridin-N-oxides of formula XXXX (reaction scheme 12) can be prepared according to known methods, such as described in Org. Synth. 4, 828 (1963); ibid. 3, 619 (1955); U.S. Pat. No. 3,047,579; and B. Iddon and H. Suschitzky in xe2x80x9cPolychloroaromatic Compoundsxe2x80x9d, Editor H. Suschitzky, Plenum Press, London 1974, page 197, a useful method being to react the pyridine derivatives of formula XXXIX with oxidizing agents, such as organic peroxy acids, for example m-chloroperbenzoic acid, peracetic acid and pertrifluoracetic acid, or aqueous hydrogen peroxide solution or hydrogen peroxide urea adduct together with carboxylic acids and/or carboxylic acid anhydrides, or inorganic peroxy acids, for example peroxymonosulfuric acid (Caro""s acid).
Suitable solvents are, for example, water, organic acids such as acetic acid and trifluoracetic acid, halogenated hydrocarbons such as dichloromethane and 1,2-dichloroethane, esters such as ethyl acetate, ethers such as tetrahydrofuran and dioxan or mixtures comprising these solvents. The reaction temperatures lie within the range of xe2x88x9220xc2x0 C. to 100xc2x0 C., depending on the solvent or solvent mixture used.
The pyridin-N-oxides of formula XXXX can be halogenated either directly according to known methods, for example with phosphorus oxychloride, phosphorus oxybromide, sulfuryl chloride, thionyl chloride or phosphorus pentachloride in phosphorus oxychloride to form the halogen pyridine derivatives of formula II (L4=halogen), or first reactedxe2x80x94likewise according to known methods (e.g. Quart. Rev. 10, 395 (1956); J. Am. Chem. Soc. 85, 958 (1963); and J. Org. Chem. 26, 428 (1961))xe2x80x94in the presence of anhydrides, for example acetic anhydride, trifluoracetic anhydride and methanesulfonic acid anhydride in a suitable inert solvent, such as halogenated hydrocarbons, for example dichloromethane and 1,2-dichloroethane, amides such as N,N-dimethylformamide and 1-methyl-2-pyrrolidone and if necessary in the presence of sodium acetate, to form the pyridol derivatives of formula XXXXI, which can then then be halogenated to form halogen pyridines of formula II, as described above for compounds of formula XXXX (L4=halogen). The reaction temperatures for this transformation reaction generally lie within the range of xe2x88x9230xc2x0 C. to 80xc2x0 C. By analogy with Tetrahedron 37, 187 (1981), antimony pentachloride (Katada reaction) presents itself as a further variant for the above transformation reaction.
The method described in the invention for the preparation of compounds of formula II 
wherein R1 and R2 are as defined under formula I, W is a W1 to W10 group, and L4 is a C1-C4alkyl or phenylsulfonyl group, is carried out starting from a compound of formula II wherein R1, R2 and W have the meanings indicated and L4 is halogen, by means of reaction with a C1-C4alkyl or phenyl thiol in the presence of a suitable base, followed by oxidation of the resulting thioether with an oxidizing agent such as hydrogen peroxide or m-chloroperbenzoic acid.
The starting compounds of formula XXXIX used in reaction scheme 12 can be prepared in a manner analogous to the methods described for compounds of formula Ia to Ik (R3=hydrogen) under reaction schemes 2 to 11.
The compounds of formulae III and VI are known or can be prepared according to known methods, as described in DE-A-3 917 469; WO 97/07114; WO 92/00976; JP-A-58-213 776; EP-A-0 012 117; EP-A-0 306 547; EP-A-0 030 215; EP-A-0 272 824; EP-A-0 500 209; U.S. Pat. Nos. 4,996,323; 5,017,705; WO 97/05112; J. Het. Chem. 11, 889 (1974); J. Het. Chem 21, 97 (1984); Tetrahedron 41, 4057 (1985); Heterocycles 22,117; Synth. 1988, 938; J. Med. Chem. 25, 96. The 2-aminopyridines of formula VI can in addition be prepared by Curtius, Hofmann or Lossen reactions from corresponding pyridine derivatives with carboxylic acid, carboxylic acid chloride, carboxylic acid azide, carboxylic acid ester or carboxylic acid amide functions in Position 2.
The reagents of formulae V, VII, X, XII, XIII, XV, XVa, XVI, XVIII, XIX, XXI, XXII, XXIVa, XXIVb, XXV, XXVa, XXVb, XXVc, XXXIV, XXVIII, XXVIIIa, XXIX, XXXI, XXXII, XXXIV, XXXV, XXXVI and XXXVII as used in reaction schemes 1 to 10 are either known or can be prepared in a manner analogous to disclosed methods.
The heterocycles of formulae W01 to W010 are either known or can be prepared in a manner analogous to known standard methods of heterocyclic chemistry.
The reactions for obtaining the compounds of formula I are advantageously carried out in aprotic inert organic solvents. Such solvents are hydrocarbons such as benzene, toluene, xylene or cyclohexane, chlorinated hydrocarbons such as dichloromethane, trichloromethane, tetrachloromethane or chlorobenzene, ethers, including diethyl ether, 1,2-dimethoxyethane, diglyme, tetrahydrofuran or dioxane, nitriles such as acetonitrile or propionitrile, amides such as N,N-dimethyl formamide, diethyl formamide or N-methylpyrrolidinone. The reaction temperatures are preferably in the range from xe2x88x9220xc2x0 to +120xc2x0 C. The reactions are usually slightly exothermic and can as a rule be carried out at room temperature. The reaction mixture can be heated for a brief time to boiling point to shorten the reaction time or also to initiate the reaction. The reaction times can also be shortened by addition of a few drops of a base as reaction catalyst. Particularly suitable bases are tertiary amines such as trimethylamine, triethylamine, quinuclidine, 1,4-diazabicyclo[2.2.2]octane, 1,5-diazabicyclo[4.3.0]non-5-ene or 1,5-diazabicyclo[5.4.0]undec-7-ene. Further suitable bases are also inorganic bases, typically hydrides such as sodium or calcium hydride, hydroxides such as sodium and potassium hydroxide, carbonates such as sodium and potassium carbonate, or hydrogencarbonates such as potassium and sodium hydrogencarbonate.
The compounds of formula I can be isolated in conventional manner by concentrating the reaction mixture and/or removing the solvent by evaporation and by recrystallizing or triturating the solid residue in a solvent in which it is not readily soluble, typically an ether, an aromatic hydrocarbon or a chlorinated hydrocarbon, or by means of column chromatography and a suitable eluent.
The compounds of formula I or compositions containing them may be used according to this invention by all standard methods of application used in agriculture, including preemergence application, postemergence application and seed dressing, as well as by different methods and techniques such as controlled release. For controlled release, a solution of the herbicide is applied to mineral granular carriers or to polymerized granules (urea/formaldehyde) and then dried. A coating can then be additionally applied (coated granules) that allows the herbicide to be released at a controlled rate over a specific period of time.
The compounds of formula I may be used as herbicides in unmodified form, i.e. as obtained in the synthesis. Preferably they are processed in conventional manner with the auxiliary agents customarily employed in formulation technology, e.g. to emulsifiable concentrates, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granulates or microcapsules. Such formulations are described, for example, in WO 97/34485 on pages 9 to 13. As with the type of agents, the methods of application such as spraying, atomizing, dusting, wetting, scattering or pouring, are selected in accordance with the intended objectives and the prevailing circumstances.
The formulations, i.e. the agents, preparations, or compositions containing the compound of formula I or at least one compound of formula I and usually one or more than one liquid or solid formulation assistant, are prepared in known manner, e.g. by homogeneously mixing and/or grinding the herbicide with said formulation auxiliaries, typically solvents or solid carriers. Surface-active compounds (surfactants) may additionally be used for preparing the formulations. Examples of solvents and solid carriers are described in WO 97/34485 on page 6.
Depending on the herbicide of formula I to be formulated, suitable surface-active compounds are nonionic, cationic and/or anionic surfactants and surfactant mixtures having good emulsifying, dispersing and wetting properties.
Examples of suitable anionic, non-ionic, and cationic surfactants are listed in WO 97/34485 on pages 7 and 8.
Also the surfactants customarily employed in the art of formulation and described, inter alia, in xe2x80x9cMcCutcheon""s Detergents and Emulsifiers Annualxe2x80x9d MC Publishing Corp., Ridgewood N.J., 1981, Stache, H., xe2x80x9cTensid-Taschenbuchxe2x80x9d (Handbook of Surfactants), Carl Hanser Verlag, Munich/Vienna, 1981, and M. and J. Ash, xe2x80x9cEncyclopedia of Surfactantsxe2x80x9d, Vol I-III, Chemical Publishing Co., New York, 1980-81 are suitable for manufacture of the herbicides according to the invention.
The herbicidal compositions will as a rule contain from 0.1 to 99% by weight, preferably from 0.1 to 95% by weight, of herbicide, from 1 to 99.9% by weight, preferably from 5 to 99.8% by weight, of a solid or liquid adjuvant, and from 0 to 25% by weight, preferably from 0.1 to 25% by weight, of a surfactant. Whereas it is preferred to formulate commercial products as concentrates, the end user will normally use dilute formulations. The compositions may also contain further ingredients, such as: stabilisers, e.g. where appropriate epoxidized vegetable oils (epoxidized coconut oil, rapeseed oil, or soybean oil); antifoams, typically silicone oil; preservatives; viscosity regulators; binders; and tackifiers; as well as fertilizers or other chemical agents.
The compounds of formula I are usually applied with success to the plants or the locus thereof in concentrations of 0.001 to 4 kg/ha, especially 0.005 to 2 kg/ha. The concentration required to achieve the desired action can be determined by experimentation. It will depend on the type of action, the development stage of the cultivated plant and of the weed, as well as on the application (locus, time, method), and as a result of these variables can vary over a wide range.
The compounds of formula I have excellent herbicidal and growth inhibiting properties, which make them suitable for application in crops of cultivated plants, especially in cereals, cotton, soybeans, sugar beet, sugar cane, plantations, rape, maize, and rice, and for the non-selective control of weeds. Crops will also be understood as meaning those crops that have been made tolerant to herbicides or classes of herbicides by conventional breeding or genetic engineering methods. The weeds to be controlled may be monocot as well as dicot weeds, typically Stellaria, Nasturtium, Agrostis, Digitaria, Avena, Setada, Sinapis, Lolium, Solanum, Echinochloa, Scirpus, Monochoda, Sagittaria, Bromus, Alopecurus, Sorghum halepense, Rottboellia, Cyperus, Abutilon, Sida, Xanthium, Amaranthus, Chenopodium, lpomoea, Chrysanthemum, Galium, Viola, and Veronica.